Isobutane stripper-depropanizer operation



Dec. 18, 1962 Filed March ll, 1960 HEIZINVLFIHOSIBG NJ L J I M I l uazlNvdoadacl l a w I l Q J Z 9 aoivuvdas m sew/Hd L j 2f t n u. o U 7, I I- v v I u --f o n. as f f l :moz I B u. Qf Nouv/www Lf I f 2 INVENTOR.

E n.0. BAUER f BY Z I a 3 Mm W j Q :J n: O L ATTORNEYS adsense isontlravrs srnirr nnnsrnorarsravn ornaariors Robert D. blader, Bartlesville, Giida., assigner to Phillips .Petroleum Company, a corporation of Delaware Filed Mar. li, web, Ser. No. idl 7 Claims. (Si. dtl-meelft;

This invention relates broadly to an improved alkylation process. ln accordance with one aspect, this invention relates to an improved process tor the separation of the hydrocarbon eiiluent in the alkylation of isoparaliinic hydrocarbons with oleiinic hydrocarbons. In accordance with another aspect, this invention relates to an improved fractionation arrangement employed for the separation of the eiiluent from an HF alltylation process wherein a low level of inerts in the process is maintained.

The catalytic alliylation of an isoparain with olefin to forni gasoline boiling range materials is well known in the art. Also, it is well known to su `ject the hydrocarbon efuent from such a process to a series of separations which generally involve fractional distillation. The separation of various fractions from the all-tylation zone hydrocarbon effluent, and particularly separation of the lighter inert materials, presents problems of considerable concern in tire industry. Also, from an economical standpoint in particular, it is desirable to recycle unreacted isoparatdn to the alkylation zone. However, with of the prior art separation systems excessive build-up of inert materials such as propane in the system is experienced due to these materials being recycled with the isoparailn. As is known in the art, the presence of inert materials in the alkylation zone appreciably decreases the efficiency of the alkylation reaction. 'he present invention is directed to an improved separation system for an alliylation hydrocarbon eiiuent wherein build-up of inerte in the system is minimised.

Accordingly, an object of this invention is to provide an improved process for the separation of materials from an alkylation Zone hydrocarbon eilluent whereby a material saving in operating and eq 'pment costs is obtained.

Another object of this invention is to minimize the build-np of inert materials in an alkylation process.

Still another object of this invention is to provide an improved process for the alkylation of isoparains with oiefins.

Other aspects, obiects as well as the several advantages of the invention are apparent ironia study et the disclosure, the drawing, the appended claims.

in accordance with the present invention, l divide the hydrocarbon eilluent recovered from an alkylation process and pass a portion of the divided eilluent to a iirst fractionation Zone wherein materials lower boiling than propane and propane are recovered overhead and removed from the process, thereby maintaining a low level of inerts such as propane in the system. The remainder of tbe divided eliduent is passed directly along with the produced depropanized bottoms from the iirst zone to a second fractionation zone or isobutane stripper. Hydrocarbon lower boiling than isobutane and isobutane are recovered overhead from the second Zone and preferably recycled directly to the alkylation zone. A bottoms fraction comprisin n-butane and alltylate can be passed to a third fractionation zone wherein a further separation of hydrocarbons is made.

By the practice of my invention, the size requirements or' my isobutane stripper or second fractionation zone can be materially decreased. Also, the build-np of inert materials, especially propane, is minimized by depropanizing only a portion of the alliylation Zone hydrocarbon eilluent.

A etter anderst riding of the present invention will be obtained upon reference to the accompanying diagrammatic ilow sheet illustrating the invention in a preferred embodiment in an HF alkylation process. Y

leie'ring now to the drawing, an olefin charge cornposed essentially of bntylenes and some propylene is passed by way of pipe lh to allrylation zone i3. Fresh isobutane in pipe il and recycle isobutane in conduit l2 are also introduced into alkylation Zone wherein, under usual alltylation conditions, alliylation ensues. Hydroiiuoric acid catalyst is introduced to alkylation zone by way of pipes 5l. and Recycle hydroiinoric acid is introduced into conduit Sil by way oi pipes dll ed. A portion of a recycle Hi: acid is passed to a rerun unit not shown by way of pipe lbe product-emulsion formed in cone l is passed to conventional settler or separator l5 by way of pipe The acid phase is removed and recovered via line and returned by pipes E19 and to alllylation Zone or contacter i3.

ln accordance with the present invention, a portion of the hydrocarbon phase recovered from separator l5 is passed by way of pipes le and if] to depropanizer 19, the overl cad ot' which is removed by way ot pipe 2li from the process. The remainder of the hydr removed from separator l5' need not be st e ted to depropanization and can bypass fractions-ttor it@ by way ot conduit A depropanizer botten stream is removed by pipe 2l and this stream combined with the stream in Jipe l, and the combined strean is passed to deisobutanizer 23 by way of conduit 22.

3y operating in accordance with iny invention, the size requirement for my deisobntanizer is materially decreased because part of the i materials are removed overhead from depropanizer 19. Also, build-up of inert inaterials such as propane is minimized in accordance with my invention since a portion of these materials is continuonsly removed from the system as overhead from depropani; r l?. The amount of hydrocarbon Tneed passed to depropan' er by way of conduit 7 will be stnhcient to rid the s'- stem of propane to maintain a low level of propane in the system. Generally, about 46% of the total hydrocarbon phase recovered from separator l5 will be subjected to depropanization. lsobiitsne and lighter materials are re ,oved overhead from deisobutanizer 23 by way of pipe i2 and recycled to all-:3 ion zone i3. Bottoms from deisobirtanizer 23 contain normal butane and alliylate is removed by conduit A portion of the deisobntanizer bottoms is passed thronbh conduit 2,5, control valve 33 introduced into heater wherein the temperature of the botto-nis fraction is increased eiiiciently to decompose organic fiuorine cornpounds present and to impart to this a quantity of heat above that required to reboil a deisobutanizer. Fthe bottoms fraction is heated in heater 2d to within a temperature range of about 325 to about 550 F. and preferably between about 375 and about 475 F.

As disclosed and claimed in copending application Serial No. 14,392, tiled March ll, 1969, a portion of the bottoms fraction heated in heating zone 26 is returned aoeaaee 3 directly to deisobutanizer 23 by way of conduits 27 and 30. The remainder of the heated bottoms fraction not returned directly to the deisobutanizer 23 is passed by way of conduits 34 and 52 to depropanizer 19 to serve as reboiler heat. The partially cooled bottoms stream is returned from depropanizer 19 by 'way of conduits 53 and to deisobutanizer 23.

Cptionally, but nevertheless, as an important feature of the above-noted application, at least a portion of the heated bottoms in conduit can be passed by way of pipe to shown in dotted lines and passed to reboiler 43. The partially cooled stream is returned from rcboiler d3 by way of control valve 45, condui and pipe t? and introduced into deiso'outanizer 23 s previously described. Control valve i5 is regulated by temperature controller da which senses the temperature in debutanizer 40.

rhe remaining portion of the bottoms fraction removed from deisobutanizer 23 not passed to heater 26 is passed by way of conduit 39 directly to debutanizer 40. Also, in accordance with the above-noted application, a vaporous side stream comprising normal butane is removed from an intermediate portion of deisobutanizer 23 by way of conduit and passed to debutanizer The amount of vaporous withdrawal is controlled by temperature or analytical controller 3S, dow controller 37 and control valve 36. A normal butane stream is recovered overhead from ebutanizer dit by way of conduit 4l. A bottom alkylate product is removed from debutanizer by way of conduit i2 and passed to reboiler 43 and a portion returned to debutanizer et? by way of conduit 5S. Alkylate product is removed from the process by way of conduit 54.

In actual operation, by removing a portion of the vaporous light materials from an intermediate portion of deisobutanizer 23 by way of conduit 35 the bubble point of the deisobutanizer bottoms passed through heater 26 is increased and therefore the bottoms stream can be heated to a higher temperature and thereby undergo a higher degree of thermal deiluorination. Also, by coolheater will be more heat than required for reboiler heat in deisobutanizer 23. The additional heat present in the eluent from furnace 216 is advantageously used as reboiler heat in either depropanizer 19 or debutanizer 40, as shown. A vaporous side stream comprising essentially normal butane is removed by conduit 3S. The amount of normal butane removed from deisobutanizer 23 is controlled by temperature controller 33 which senses the column temperature. The column temperature will vary depending upon the amount of Vaporous material returned by conduit 30 and condensed in column 23 to give up its latent heat.

rthe following is a specific example or operation according to the above description.

1;) ln a specilic example using my process, the contactor 13 is operated at 90 F., and at a pressure suliicient to maintain a liquid phase. The isobutane to olefin mole ratio is 5:1, and the volume ratio of hydrocarbon to catalyst is 1:1. Each barrel of olen reacts with 1.3

2a barrels of isobutane to produce 1.7 barrels of total alkylate. The ollein stream is introduced at F., the recycle acid at 90 F. and the isobutane at 90 F. The separator surge is operated at 90 F., and pressure to maintain liquid phase.

Nora-Fired heater, 26; outlet pressure, 340 psig.; outlet teinperature, lo

in the following table, the composition of the various ing at least a portion of the eluent from heating zone i9 iiow streams shown on the drawing are tabulated.

Table Stream No 10 11 12 16 17 18 21 22 39 24 27 52 30 35 20 11 54 Direct Tomi Rcac- Por4 Isofuremi; to Depto Reeytor Charge tion to Depro- Charge Isobutano nace '9m reboil pa- Debu- Debu- Stream B/D Olen Fresh ele hydroto deisobu pato isobutano botei'hu- 'to deso- Side nizer tanizertanizor component charge isobuisobucarbon propatano nizer butano bottom to ent to Tabou butadraw overoveralkytaue tane ol'ilumeer stripbotstripper tom furisooudprm meer head head late ent per toms yield nace tane pw colyield yield yield strip- Dizer umn per tower C3- 1, 45 C3 1,221 50 2,520 ,070 1,533 2,413 rotfl" ifi ii iif ii' fs' 5s iso 1104. 175 0,613 8,545 3,295 5, 250 956 2, 988 lOl-, 100 250 855 330 525 1, 600 5, LA. 20 7, 660 2, Q54 4,706 21,997 68,742 HA. 405 156 24.9 16 ,645 HF-. 221 359 138 221 (l) Total 10,080 4,397 50, 647 63,025 24,303 38,722 22, G87 61,409 8,982 80, 838 54,971 25,867 80,838 1,780 1,616 2,022 8,740

l Not measurable as barrels, present as ppm. fluorides.

Z6, as shown, higher circulation rates and temperatures on the deisobutanizer bottom stream being heated can be obtained thereby improving thermal detluorination.

Assuming feed to tower 23 to increase at a constant quality, the tower bottom temperature will begin to lower. T his, via temperature controller El, will actuate ilow controller 31! to eiect further opening of valve 33, which, in turn, increases the amount of bottoms fed to heater 26. As additional bottoms material is passed through furnace 26, additional fuel is charged to the furnace in response to the furnace erliuent temperature, and additional vaporization of liquid takes place in heater 26. The amount of heat imparted to the bottoms fraction passed through the 2 Negligible tluorides.

These data illustrate a specific plant operation wherein of the 63,025 barrels per day hydrocarbon eilluent from do separator 15, 24,303 barrels per day are charged to the depropanizer to remove i616 barrels per day light materials (propane and lighter), and the remaining 38,722 barrels per day plus 22,687 barrels per day depropanizer bottoms are charged combined to the isobutane removal column.

Among the advantages of operating according to this specific example of my invention as compared to the prior art and methods are that a much smaller isobutane removal column can be employed while maintaining low quantity oi these light inert hydrocarbons in the recycle isobutane and, hence, low quantity of these inerts in the alkylation system, such low quantities being essential for efficient operation.

lt will be understood by one skilled in the art in possession of this disclosure that the drawing is essentially schematic in character and that certain pieces of equipment and/or details thereof have been omitted for the sake of simplicity. Such details will be routinely supplied by one skilled in the art in possession of this disclosure. Furthermore, detail conditions of operation as they may apply to certain embodiments of the invention which can be routinely supplied by one skilled in the art, have not been herein elaborated also for sake of simplicity.

While preferred embodiments of this invention have been disclosed, the description is intended to be illustrative only and it is to be understood that changes and variations can be made without departing from the spirit and scope of the invention as defined by the appended claims.

l claim:

l. An improved process for the separation of the hydrocarbon eiuent from an alkylation process which comprises passing a portion of said eiliuent to a rst separation zone wherein lower boiling materials are separated overhead and removed from the process, thereby minimizing the build-up of inerts in the process, removing from a lower portion of said rst zone a liquid hydrocarbon portion reduced in lower boiling materials, passing said liquid fraction and the remainder of said efiiuent to a second separation zone wherein isoparafn is separated overhead, and withdrawing a second liquid hydrocarbon fraction from a lower portion of said second zone as a product of the process.

2. Process according to claim 1 wherein overhead from said rst zone comprises propane.

3. Process according to claim 2 wherein said isoparain is isobutane.

4. An improved process for the separation of the hydrocarbon eiuent `from an `alkylation process which comprises dividing said eiuent, passing a portion of said effluent to a iirst fractionation Zone wherein materials lighter than propane and propane are recovered overhead and removed from the process, thereby maintaining a low level of propane in the process, withdrawing from a lower portion of said iirst Zone an at least partially depropanized liquid hydrocarbon fraction, passing said depropanized fraction and the remainder of said effluent directly to a second fractionation zone wherein isoparaffin is separated overhead and recycled `to said alkylation, withdrawing an at least partially deisobutanized liquid hydrocarbon fraction from a lower portion of said second zone, and passing said deisobutanized fraction to a third fractionation zone wherein a further separation of hydrocarbons is made.

5 Process according to claim 4 wherein said alkylation is carried out in the presence of a hydrouoric acid catalyst.

6. Process according to claim 5 wherein said isoparaffin is isobutane.

7. A process which comprises introducing a portion of the hydrocarbon eiliuent from the alkylation of a low boiling olefin with isobutane in the presence of a hydrouoric acid catalyst into a rst yfractionation zone wherein hydrocarbons lower boiling than propane and propane are separated overhead and removed from the process, thereby maintaining a low level of propane in the process, withdrawing from a lower portion of a said iirst zone a depropanized liquid hydrocarbon fraction, combining said depropanized fraction and the remainder of said eiiiuent, introducing said combined fractions directly into a second fractionation zone wherein isobutane is separated overhead and recycled to said aikylation, withdrawing from a lower portion of said second zone a deisobutanized liquid hydrocarbon fraction, and passing said deisobutanized fraction to a third fractionation Zone wherein a further separation of hydrocarbons is made.

References Cited in the iile of this patent UNITED STATES PATENTS 2,342,364 Parker Feb. 22, 1944 2,363,171 Francis Nov. 21, 1944 2,382,067 Karel Aug. i4, 1945 2,542,927 Kelley Feb. 20, 1951 2,865,971 Beavon Dec. 23, 1958 2,938,061 Smith May 24, 1960 

1. AN IMPROVED PROCESS FOR THE SEPARATION OF THE HYDROCARBON EFFLUENT FROM AN ALKYLATION PROCESS WHICH COMPRISES PASSING A PORTION OF SAID EFFLUENT TO A FIRST SEPARATION ZONE WHEREIN LOWER BOILING MATERIALS ARE SEPARATED OVERHEAD AND REMOVED FROM THE PROCESS, THEREBY MINIMIZING THE BUILD-UP OF INERTS IN THE PROCESS, REMOVING FROM A LOWER PORTION OF SAID FIRST ZONE A LIQUID HYDROCARBON PORTION REDUCED IN LOWER BOILING MATERIALS, PASSING SAID LIQUID FRACTION AND THE REMAINDER OF SAID EFFLUENT TO A SECOND SEPARATING ZONE WHEREIN ISOPARAFFIN IS SEPARATED OVERHEAD, AND WITHDRAWING A SECOND LIQUID HYDROCARBON FRACTION FROM A LOWER PORTION OF SAID SECOND ZONE AS A PRODUCT OF THE PROCESS. 